Rinaldo's disguise being fake glasses and mustache, presumably worn over his real mustache, and papers with the pseudonym of Filet Mignon.
Anne trying her very best to appear as Hellspawn by speaking abyssal and making her eyes glow with Thaumaturgy, and Lonnegan's simply baffled reaction.
At one point, Anne uses her knife collection to fastidiously bar all of the exits to a tavern with a large number of civilians and several members of the Stonerotten inside. While Rinaldo still thinks they're going to interrogate the Stonerotten members, Anne immediately sets the building on fire once she's finished barring the exits.
Rinaldo attempting to bargain with the gate guards through the door, their only response being to slide a wanted poster with Rinaldo's exact likeness under the door.
Season 2
Vinnie's performance of "Wonderfrog."
Every member of the party but Vinnie attempting (and mostly failing) to hide behind the same tree, ending up in a pile with Violet on top.
Violet then tries to get up and stand defiantly next to Vinnie, but screws that up too and gets her horn stuck in the ground.
Zavala(In a baby voice): I wanna pwotect my village.
Vinnie:Billy my good bitch! How dare you!
Sherry's deepest heart's desire is a mountain of sandwiches.
Season 3
Crab day. Perhaps funniest of all is the fact that Winifred takes Dora's Crab Day almost as seriously as she does.
The simple voice of Bumbershoot Von Victrola is enough to make the call just stop for almost two whole minutes.
Rolen referring to the skeleton guards - all with Papyrus as Roll 20 icons - as "gentlebones". And all of Skitch's following skeleton madness.
In episode 3, Bumbershoot's assessment of the mission:
Bumbershoot: Okay, so this is what I've learned so far: Garrick is an asshole.
Zoey's wild magic rolls lead to many of the season's best moments.
Zoey's very first magic roll mistakenly summons a hostile elemental monster, causing Quinn to immediately have a giggling panic attack.
And the roll immediately afterwards, which teleports her into the mansion she was trying to get into... but then causes her to immediately fall unconscious and loudly knock over the vase she was hiding behind.
Zoey's magic causing her to constantly emit polka music
Zoey growing a tail is funny, but this exchange makes it even better.
Zoey: "also I have a tail now"
Alice Hawthorne: in genuine shock and despair "Oh merciful Neptune!"
Zoey being forced to speak in rhyme, and when she tries to circumvent it...
Zoey's note: Damn this magic is really biting, it even works, even in writing.
During the otherwise dramatic fight with Lady Nim Zoey's magic causes her to summon a shark which promptly crushes Nim.
Her accidentally creating a giant tree inside Hawthorne house, causing Dora to comment that it's technically a treehouse now.
Doubles as a Moment of Awesome but during her second fight with Dora she becomes magnetic and rolls "MAX STRENGTH" on the table (written exactly like that).
At the beginning of Episode 13, Catarina decides to shoot Memphis, one of the Crown Corporation's executives, in the head with a non-damaging bullet primed with a Detect Thoughts spell out of nowhere during a meeting with him in a nightclub. Despite not actually hurting Memphis, the gunfire causes the bouncer (and the rest of the party, who were not expecting her to do what she did) to try to grapple her, and the resulting struggle immediately devolves into a comedy of errors, as Lenora tries to tackle her and gets swatted to the ground, the bouncer successfully tackles her and melts her gun with fire breath, Frank jumps on top of the bouncer to try to help subdue Catarina, and Eddi casts a sleep spell which accidentally hits Frank instead.
Austin: To recap: Catarina comes back into the room where you guys are planning the next heist, shoots Memphis in the head with a Detect Thoughts bullet, finds out that he's more scared of you than you are of him, and then there's a dogpile in the middle of the room which culminates in Frank being magically put to sleep on top of the dogpile, smooshing everyone beneath him with his dad bod.
During a boss fight in Episode 17, the boss gets high on Nox, marking the first time in the season that an NPC had been under the influence. As a result, Austin keeps forgetting to factor the effects of Nox into his rolls (specifically, that anyone under the influence gets advantage on any roll)... at least, until Quinn reminds him. This newfound advantage keeps negating what would otherwise have been successful attacks against the boss, much to Lauren's frustration.
Halfway through Episode 19, the scene cuts to Catarina attacking a zeppelin as part of her rampage against the Crown Corporation directors. Quinn's rolls during the fight are so consistently good (as well as Austin's rolls while controlling the NPCs being mediocre at best and laughably bad at worst) that it reaches the point of absurdity, to the point where even Austin becomes incredibly frustrated at how the fight is progressing.
The final opponent, equally fed up with how the fight is going, ends up throwing himself to his death, crotch chopping the whole way down. Later the party find an Impact Silhouette where he landed.
Episode 20:
Catarina attempts to inflitrate the Manufacturing branch disguised as a mild-tempered old woman with a stereotypical British accent. She keeps up the disguise even after stealth fails, resulting in her engaging in incredibly brutal combat while still playing her role, culminating when she snaps a guard's neck in front of some of the other guards in an attempt to intimidate them.
Catarina(in a very shrill, proper British accent): Do you want some of this, motherfuckers?!
In the same fight, Quinn engages in some very successful Rules Lawyering (with a side of Exact Words) to get into the panic room to assassinate the head of Manufacturing, much to Austin's frustration.
Quinn: Oh, hold on a second. I'm going to punch in the code for the door.
Austin: ...Okay. And how do you figure you have that?
In the first half of Episode 5, the party's luck turns sour in spectacular fashion. Over the course of just a few minutes, due to a series of botches, Liamoira almost accidentally starts an Animal Stampede of Tarrasques (which was prevented only by a Critical Success on a Survival roll on Dregg's part), Olivia decides that the best way to pacify a Tarrasque is blind it, and when the blind Tarrasque starts charging, Dregg botches a Strength check to throw Liamoira out of the way (in addition, while not botches, Sasha fails a strength check of her own to rescue Olivia, Dregg still manages to fail the reroll when Liamoira uses her Conduit of Spirits to allow both Sasha and Dregg to redo their rolls, and both Olivia and Liamoira fail Deception checks— twice, in Liamoira's case). It's only due to Sasha's quick thinking and Dregg finally passing a Deception check that the party avoids a unceremoniousTotal Party Kill.
In Episode 23, Big Star jokingly says, "Give me your money," to some babies. Seemingly electrified by the thought of crime, Sasha screams, "Yeah! And give us your shoes!"
When Melbeck and Dregg get into the second level of the Purist Compound, they reason that they need to escalate their shows of dedication to their conduits, while Melbeck just summons some spirits to heal everyone nearby, Dregg decides to barricade the bathroom and beat up anyone who tries to go in.
Ambassador Respect, the Solitaire voiced by Quinn, given a Snagglepuss-esque voice. Made even funnier by his death, wielding 10 pistols against slug monsters.
During the second fight with Keyser, the party is struggling to figure out how to defeat him without his Conduit killing them as well. Quinn decides to just shoot him, causing an argument to break out between him and the others which ends with him reluctantly healing Sasha. Conrad then points out that they can just remove his Conduit which Austin responds to with "Fuck, shut up!" Even better, Quinn immediately ignores this and instead tries to attack Kayser again instead of removing his Conduit, starting another argument.
Season 6:
King Badass, whenever nothing else is going on, will pull out a book of conversation starters and awkwardly ask the party members questions.
At one point he loses the book and can't handle talking without it, only to find out that it was just in his other pocket the whole time.
Blake Ferris distracting the Mettatron with a ridiculously dull monologue about the importance of colonoscopies.
When the party fights a stairwell of angels Quinn becomes convinced that the angels have to be really small to fit and tries to have King blow them away, to Austin's confusion. Later when Nyfix's Triceratops form is too big for the stairwell Quinn becomes even more perplexed, calling it a "Chinese puzzlebox of a staircase."
Cordelia proposing her girlfriend become the new ruler of the Abyss and the new Mettatron in the same episode.
In that same episode Cordelia turns a simple assassination for Blake where she disguises herself as the bride of her target at his wedding into a disaster that ends with Blake sliding down an infinite slope with a dying Cordelia and the groom's stone corpse and everyone at the wedding dead, except the real bride who was in the bathroom.
In the Gotterdammerung Grand Prix, the safeword to get teleported out of danger is "Pineapple" and at one point King goes up to Cordelia and asks her "what topping goes well on pizza with ham?" Resulting in a very embarrassing elimination from the race.
In the Gotterdammerung Grand Prix a bunch of characters have weird mounts and what's Bake's? A giant Seagull that he controls with a french fry on a fishing pole.
When Austin explains that Blake and Cordelia's next target is a Yagnoloth the discussion quickly turns into a debate on how the thing masturbates ultimately concluding that it's inability to do so is it's curse.
The assassination itself has Cordelia busting into the funeral of their previous target pretending to be his mistress. She calls the widow Jessica and when it turns out that isn't her name says, "he didn't even love you enough to tell me your real name!"
In the final episode during the fight between Nifyx Cordelia and Blake, the players randomly start asking Austin for advantage on rolls for the flimsiest of reason, to his hilarious annoyance.
Season 7
Continuing on from the end of last season, all the players continuously ask Austin for advantage on rolls for increasingly flimsy reasons, causing him to threaten to give them disadvantage for asking.
This season randomly has some of the absolute worst die rolls in the show's history, with player continuously botching rolls and falling into danger at every step. Later the luck gets even crazier when groups rolls continuously have crits and botches in them (called a "crit botch" or a "crotch"), leading to even more insane situations.
Sabrina playfully throwing a ball of salt at Khorton leads to Vindrass botching a roll to take the hit for him, leading to Austin making her fall through a layer of salt and getting impaled on a narwhal skeleton causing Lauren to ask what the hell is wrong with Austin for escalating the situation so much.
Poor Vindrass walking into a room and getting getting immediately kidnapped because of a botched investigation roll three separate times.
During an episode where the players control the NPC members of the Wolfpack, Quinn gives Yeung a squeaky Morty-esque voice and turns their nervousness up to eleven when they throw up mid conversation out of sheer anxiety. Quinn also turns up the Thri-kreen's propensity for eating heads when Yeung drops everything they're doing mid fight to nervously eat a dead Mook.
When the Wolfpack is attacked by a group of empowered halflings inside a mall, the halflings take objects from the various stores as clothes, including a mascot outfit of a walking smoothie with a stethoscope named "Dr. Smooth." Even better, that halfling survives and decides to keep wearing the outfit for the rest of the season.
After a big fight, the players randomly get sidetracked and get into a ridiculously long discussion about Chuck Palahniuk and how Turkish Delight isn't nearly as good as C. S. Lewis makes it sound which goes on for so long that Austin names the episode after it.
During one of Frida's flashback sequences she builds a makeshift flamethrower and uses it on the Deacon. Later Lola gets ahold of the discarded flamethrower and uses it on the Deacon.
The Deacon: HOW DOES THIS KEEP HAPPENING?! DOES EVERY BITCH IN THIS COUNTRY HAVE A FUCKING FLAMETHROWER?!
Near the end of the season Duke Pendergrass almost falls to his death and Austin says "Oh no!" in his Ukranian accent which Joa and Lauren find so funny they both continuously ask him to say it again for the rest of the season.
Season 8
Right off the bat it's clear Austin wants to limit the number of NPCs this season but this becomes increasingly funny as the players keep introducing more and more animals that they can talk to with magic, all of which are ridiculous.
Drip, a fashion, obsessed shark-horse who gets more and more ridiculous outfits as the season progresses.
The tum-tums, tiny balls of fur which live off smells.
Cat a Myrmecoleon (lion sized ant with a lion head).
Nobie, Phillipa's pet sheep who's initially convinced he's a god and gets the tum tums to worship him.
The Pizza Rats, a bunch of rats whose appearance always causes the players to put on ridiculous Italian accents.
Basil, the unicorn created by the Genius' magic and who speaks in a gruff London accent and has limited Reality Warper powers.
When Neelix accidentally releases the Genius' robots he designed to help the town citizens in their jobs, the one designed for Pastor Vary, instead just stands outside his hous flipping it off.
When Cat is Promoted to Playable and given the ability to talk, he quickly imprints on Slime as his "mother" and asking her for advice with any confusing thoughts he has, to which she responds by, explaining that his thoughts are just neurochemicals. Throughout the rest of the season Cat refers to all of his emotions as neurochemicals as a result.
When the party meets Mold, a part of Silme that Cat cut off which developed its own personality, they starts calling Sime and Cat their mother, causing Cat endless confusion as he tries to wrap his head around being the mother of a piece of his mother. This isn't helped by Slime trying to reassure him by saying that if Mold absorbs her, she'll still be there with Cat, just without her normal personality and being physically a part of an evil version of herself, which unsurprisingly stresses poor Cat out even more.
the discussion quickly turns into a debate on how the thing masturbates ultimately concluding that it's inability to do so is it's curse.